Construction of plasmon-based nanostructures is an effective way to enhance the photo catalytic activities of semiconductor photocatalysts for water-splitting. However, the synergistic effect of plasmon-related hot electrons and holes for water splitting in the plasmon-hybrid photocatalyst is rarely considered. Herein, we construct a plasmon-based Au/LaFeO3 composite photocatalyst to investigate the complex roles of hot electrons and holes for solar water splitting. Benefiting from the formation of Schottky junction and surface plasmon resonance effect of the Au nanoparticles, the synthesized photocatalyst exhibits an excellent photocatalytic activity for each half-reaction of water splitting, and the rates for H-2 and O-2 generation are obtained as high as 202 mu mol g(-1) h(-1) and 23 mu mol g(-1) h(-1), respectively. Moreover, an in-depth investigation reveals that the improved hydrogen evolution is caused by the hot electron injection from Au to LaFeO3, and the hot holes in Au induced by the separation of hot charges can initiate the water oxidation directly on the surface of gold. Thus, this work provides a new insight into the synergistic effect of plasmon-related hot electrons and holes for boosting the photocatalytic reactions. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.